A polymorph of butobarbital with two distinct hydrogen-bonding motifs

N-H...O bonding in a form of 5-butyl-5-ethyl­barbituric acid (systematic name: 5-butyl-5-ethyl-1,3-diazinane-2,4,6-trione), C₁₀H₁₆N₂O₃, produces two distinct one-dimensional motifs, viz. tape and ladder. Both are different from the ribbon chain motif observed in two previously reported polymorphs of the same compound.

S1. Comment

Butobarbital, (I), is a 5,5-disubstituted barbituric acid derivative used as a sedative hypnotic drug for severe insomnia (Soneryl; Joint Formulary Committee, 2007). Cleverley & Williams (1959) reported the existence of four polymorphic forms, and Draguet-Brughmans et al. (1981) investigated the physical properties of three modifications of (I). Their form I (m.p. 397 K) is consistent with a crystal structure reported earlier by Bideau (1971). Recently, Nichol & Clegg (2005) determined the structure of a low-temperature (LT) phase, which was obtained by cooling a crystal of form I (crystallized from water) to 120 K. A subsequent data collection at room temperature showed that this phase transition is reversible. The arrangement of butobarbital molecules in these two structures is practically the same, and a conformational change of the n-butyl groups was identified as being their main difference.

The structure of a third polymorph of (I) with prismatic habit is reported here. Comparison with previous studies on the polymorphism of (I) (Bideau, 1971; Draguet-Brughmans et al., 1981; Cleverley & Williams, 1959; Williams, 1959; Mesley & Clements, 1968; Mesley, 1969; Huang & Jerslev, 1951) shows that the data (IR-spectrum and X-ray powder pattern) for this modification match closely with those given by Draguet-Brughmans et al. (1981) for their polymorph II.

The title structure has the space group P2₁/c and four independent molecules, one of which is shown in Fig. 1. A l l molecules adopt the same principal geometry, and their alkyl chains exhibit the expected staggered antiperiplanar conformation. The bond lengths and angles are consistent with the corresponding parameters in the previously reported modifications of (I). The six-membered rings are not perfectly planar.

Two of the molecules of (I) are joined into N—H···O-bonded tapes (Fig. 2a and Table 1) by employing two hydrogen-bond donor and two acceptor functions per molecule. These tapes consist of two independent R³₃(12) rings (Bernstein et al., 1995), which connect three molecules. The rings are edge-fused to larger R⁴₄(18) units. The mean plane through the alkyl fragment of (I) is approximately perpendicular with respect to the central plane of the tape defined by the C₄N₂ rings, so that angles of 87.08 (9) and 82.65 (8)° are formed. All ethyl moieties point in one direction and all butyl groups in the opposite direction.

N—H···O interactions between the other two independent molecules result in the ladder motif shown in Fig. 2(b). Pseudo-centrosymmetric dimers with R²₂(8) rings are edge-fused with pseudo-centrosymmetric R⁴₄(18) rings connecting four molecules. Both tapes and ladders propagate parallel to the a axis, which implies a perfect match of their translation periods. Furthermore, the four independent molecules are arranged in separate one-dimensional stacks parallel to the a axis.

A closer inspection reveals a set of short dimeric C—H···O contacts (Table 1), which connect adjacent ladders related by inversion symmetry. These contacts involve a butyl CH₂ group and an O atom not engaged in classical hydrogen bonding. The packing of tapes and ladders is depicted in Fig. 3.

Ribbon chains are the most common hydrogen-bonding motifs in 5,5-substituted derivatives. The chains found in form I of butobarbitul and its LT-form (Bideau, 1971; Nichol & Clegg, 2005) belong to this particular class. By contrast, there are only two previous examples of the tape motif shown in Fig. 2(a), the structures of γ -methylamobarbital (Gartland & Craven, 1971) and quinal barbitone (Nichol & Clegg, 2007). The ladder motif of Fig. 2(b) has been observed in methylphenylbarbital (Bravic et al., 1968) and barbital (Craven et al., 1969). Thus, the polymorph of (I) reported here is the first example where these two rather unusual one-dimensional motifs appear simultaneously in one structure.

Related literature

(type here to add)

For related literature, see: Bernstein et al. (1995); Bideau (1971); Bravic et al. (1968); Cleverley & Williams (1959); Craven et al. (1969); Draguet-Brughmans, Draux & Bouche (1981); Gartland & Craven (1971); Huang & Jerslev (1951); Joint (2007); Mesley (1969); Mesley & Clements (1968); Nichol & Clegg (2005, 2007); Williams (1959).

S2. Experimental

Single crystals were taken from an approximately 40 year-old commercial product ("Soneryl, 5-n-butyl-5-aethyl-barbituricum"; Interpharm Kom.-Ges. Vienna), which also contained the form I described by Bideau (1971).

S3. Refinement

All H atoms were identified in a difference map. CH₂ hydrogen atoms were positioned geometrically with C—H = 0.99 Å (CH₂). Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip with C—H = 0.98 Å (CH₃). Hydrogen atoms attached to N were refined with constrained distances N—H = 0.97 (1) Å. The U_iso parameters were U_iso(H) = 1.2 U_eq(N or C) for NH, CH₂ or U_iso(H) = 1.5 U_eq(C) for CH₃.

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

	Fig. 1. : One of the four independent molecules of butobarbital, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% level.
	Fig. 2. : One-dimensional H-bonding motifs: (a) tape and (b) ladder.
	Fig. 3. : The packing of the hydorgen-bonded tapes (T) and ladders (L), viewed parallel to the translation vector of each chain (along the a axis). The four independent molecules are drawn in different colors.

5-butyl-5-ethyl-1,3-diazinane-2,4,6-trione

Crystal data

C10H16N2O3	F(000) = 1824
Mr = 212.25	Dx = 1.253 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 33142 reflections
a = 6.8534 (1) Å	θ = 2.9–27.5°
b = 29.6631 (7) Å	µ = 0.09 mm^−1
c = 22.2107 (5) Å	T = 120 K
β = 94.408 (1)°	Prism, colourless
V = 4501.93 (16) Å^3	0.20 × 0.07 × 0.07 mm
Z = 16

Data collection

Bruker–Nonius KappaCCD diffractometer	7853 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	5428 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 9.091 pixels mm^-1	θmax = 25.1°, θmin = 3.0°
ϕ & ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −35→35
Tmin = 0.896, Tmax = 0.994	l = −26→25
27772 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.P)^2 + 8.8472P] where P = (Fo^2 + 2Fc^2)/3
7853 reflections	(Δ/σ)max < 0.001
573 parameters	Δρmax = 0.26 e Å^−3
8 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O11	0.4089 (3)	0.45787 (7)	0.18105 (12)	0.0333 (6)
O12	0.4119 (3)	0.60900 (7)	0.16129 (12)	0.0328 (6)
O13	0.9996 (3)	0.54083 (7)	0.17596 (10)	0.0277 (6)
N11	0.4146 (4)	0.53348 (9)	0.17523 (12)	0.0199 (6)
H11	0.2745 (16)	0.5352 (11)	0.1755 (14)	0.024*
N12	0.7041 (4)	0.57359 (8)	0.16696 (12)	0.0216 (6)
H12	0.767 (4)	0.6018 (6)	0.1591 (14)	0.026*
C10	0.7279 (4)	0.49118 (10)	0.18540 (14)	0.0190 (7)
C11	0.5058 (4)	0.49207 (11)	0.17982 (14)	0.0210 (7)
C12	0.5034 (5)	0.57422 (10)	0.16748 (14)	0.0207 (7)
C13	0.8228 (4)	0.53657 (10)	0.17542 (14)	0.0194 (7)
C14	0.7958 (5)	0.47544 (11)	0.25019 (14)	0.0234 (8)
H14A	0.7416	0.4451	0.2569	0.028*
H14B	0.9402	0.4730	0.2538	0.028*
C15	0.7328 (5)	0.50711 (12)	0.29894 (15)	0.0296 (8)
H15A	0.7897	0.5370	0.2935	0.044*
H15B	0.7783	0.4953	0.3388	0.044*
H15C	0.5897	0.5094	0.2960	0.044*
C16	0.8019 (5)	0.45765 (11)	0.13910 (15)	0.0252 (8)
H16A	0.9461	0.4555	0.1456	0.030*
H16B	0.7474	0.4275	0.1468	0.030*
C17	0.7481 (5)	0.47025 (11)	0.07333 (15)	0.0288 (8)
H17A	0.6040	0.4696	0.0654	0.035*
H17B	0.7929	0.5014	0.0661	0.035*
C18	0.8394 (5)	0.43838 (13)	0.02989 (15)	0.0339 (9)
H18A	0.7924	0.4074	0.0367	0.041*
H18B	0.9833	0.4385	0.0386	0.041*
C19	0.7913 (6)	0.45093 (13)	−0.03593 (16)	0.0411 (10)
H19A	0.6491	0.4505	−0.0450	0.062*
H19B	0.8523	0.4292	−0.0619	0.062*
H19C	0.8414	0.4812	−0.0434	0.062*
O21	−0.1150 (3)	0.80457 (8)	0.13937 (12)	0.0347 (6)
O22	−0.1010 (3)	0.65261 (7)	0.13294 (11)	0.0327 (6)
O23	0.4811 (3)	0.72318 (8)	0.13967 (12)	0.0340 (6)
N21	−0.1040 (4)	0.72900 (9)	0.13573 (12)	0.0216 (6)
H21	−0.2449 (15)	0.7286 (11)	0.1330 (14)	0.026*
N22	0.1901 (4)	0.68898 (9)	0.13797 (13)	0.0243 (6)
H22	0.255 (4)	0.6600 (6)	0.1372 (14)	0.029*
C20	0.2063 (4)	0.77216 (11)	0.14474 (15)	0.0232 (7)
C21	−0.0153 (5)	0.77063 (11)	0.13958 (15)	0.0243 (8)
C22	−0.0117 (5)	0.68777 (10)	0.13557 (15)	0.0211 (7)
C23	0.3050 (5)	0.72668 (11)	0.14013 (15)	0.0242 (8)
C24	0.2738 (5)	0.79210 (11)	0.20747 (15)	0.0289 (8)
H24A	0.4183	0.7945	0.2108	0.035*
H24B	0.2200	0.8229	0.2103	0.035*
C25	0.2114 (6)	0.76443 (13)	0.26039 (16)	0.0376 (9)
H25A	0.0682	0.7629	0.2586	0.056*
H25B	0.2608	0.7787	0.2984	0.056*
H25C	0.2649	0.7339	0.2583	0.056*
C26	0.2740 (5)	0.80264 (11)	0.09376 (15)	0.0264 (8)
H26A	0.2209	0.8334	0.0985	0.032*
H26B	0.4186	0.8048	0.0977	0.032*
C28	0.2751 (5)	0.81423 (13)	−0.01923 (17)	0.0364 (9)
H28A	0.4190	0.8119	−0.0199	0.044*
H28B	0.2423	0.8461	−0.0114	0.044*
C27	0.2085 (5)	0.78516 (11)	0.03105 (15)	0.0285 (8)
H27A	0.2604	0.7543	0.0266	0.034*
H27B	0.0639	0.7833	0.0271	0.034*
C29	0.1795 (6)	0.80027 (14)	−0.08044 (17)	0.0415 (10)
H29A	0.2057	0.7683	−0.0874	0.062*
H29B	0.2334	0.8184	−0.1121	0.062*
H29C	0.0380	0.8052	−0.0812	0.062*
O31	0.5448 (3)	0.44572 (8)	0.47631 (11)	0.0318 (6)
O32	0.4867 (3)	0.38779 (7)	0.28810 (10)	0.0227 (5)
O33	−0.0751 (3)	0.41582 (7)	0.37462 (10)	0.0238 (5)
N31	0.5111 (4)	0.41805 (9)	0.38188 (12)	0.0207 (6)
H31	0.6511 (16)	0.4178 (11)	0.3811 (14)	0.025*
N32	0.2053 (4)	0.40448 (8)	0.33111 (12)	0.0180 (6)
H32	0.132 (4)	0.3908 (9)	0.2971 (9)	0.022*
C30	0.2156 (4)	0.44125 (11)	0.43190 (14)	0.0190 (7)
C31	0.4361 (5)	0.43521 (10)	0.43308 (15)	0.0208 (7)
C32	0.4069 (4)	0.40266 (10)	0.33071 (14)	0.0170 (7)
C33	0.1032 (4)	0.41922 (10)	0.37796 (14)	0.0184 (7)
C34	0.1447 (5)	0.42132 (11)	0.49040 (15)	0.0271 (8)
H34A	0.2058	0.4383	0.5253	0.032*
H34B	0.0013	0.4254	0.4900	0.032*
C35	0.1925 (6)	0.37162 (12)	0.49886 (17)	0.0389 (9)
H35A	0.1349	0.3546	0.4641	0.058*
H35B	0.1386	0.3607	0.5358	0.058*
H35C	0.3348	0.3675	0.5022	0.058*
C36	0.1690 (5)	0.49232 (10)	0.42909 (15)	0.0222 (7)
H36A	0.0254	0.4962	0.4286	0.027*
H36B	0.2279	0.5066	0.4665	0.027*
C37	0.2403 (5)	0.51727 (11)	0.37543 (15)	0.0272 (8)
H37A	0.1836	0.5029	0.3378	0.033*
H37B	0.3844	0.5144	0.3763	0.033*
C38	0.1867 (5)	0.56717 (11)	0.37406 (16)	0.0322 (9)
H38A	0.2490	0.5820	0.4106	0.039*
H38B	0.0432	0.5702	0.3751	0.039*
C39	0.2513 (7)	0.59100 (13)	0.31810 (18)	0.0487 (11)
H39A	0.3945	0.5912	0.3193	0.073*
H39B	0.2027	0.6221	0.3172	0.073*
H39C	0.1981	0.5750	0.2818	0.073*
O41	−0.0231 (3)	0.30944 (8)	0.03221 (10)	0.0291 (6)
O42	0.0260 (3)	0.37074 (7)	0.21871 (10)	0.0240 (5)
O43	0.5907 (3)	0.34467 (8)	0.13256 (10)	0.0286 (6)
N41	0.0047 (4)	0.33963 (9)	0.12537 (12)	0.0205 (6)
H41	−0.1347 (16)	0.3417 (11)	0.1272 (14)	0.025*
N42	0.3087 (4)	0.35762 (9)	0.17445 (12)	0.0203 (6)
H42	0.374 (4)	0.3707 (10)	0.2100 (9)	0.024*
C40	0.3037 (5)	0.31454 (11)	0.07903 (14)	0.0219 (7)
C41	0.0821 (5)	0.32123 (10)	0.07547 (15)	0.0208 (7)
C42	0.1089 (4)	0.35673 (10)	0.17564 (14)	0.0195 (7)
C43	0.4127 (5)	0.34084 (10)	0.12938 (14)	0.0213 (7)
C44	0.3833 (5)	0.32688 (12)	0.01816 (15)	0.0298 (8)
H44A	0.5259	0.3210	0.0206	0.036*
H44B	0.3210	0.3071	−0.0137	0.036*
C45	0.3472 (5)	0.37585 (13)	−0.00012 (16)	0.0359 (9)
H45A	0.2062	0.3812	−0.0071	0.054*
H45B	0.4108	0.3822	−0.0373	0.054*
H45C	0.4016	0.3957	0.0322	0.054*
C46	0.3426 (5)	0.26358 (11)	0.09195 (15)	0.0266 (8)
H46A	0.2731	0.2460	0.0590	0.032*
H46B	0.4844	0.2580	0.0900	0.032*
C47	0.2823 (5)	0.24518 (11)	0.15202 (15)	0.0279 (8)
H47A	0.3460	0.2633	0.1854	0.034*
H47B	0.1390	0.2485	0.1533	0.034*
C48	0.3374 (5)	0.19599 (11)	0.16174 (16)	0.0329 (9)
H48A	0.4816	0.1932	0.1637	0.040*
H48B	0.2829	0.1783	0.1266	0.040*
C49	0.2640 (6)	0.17618 (13)	0.21891 (18)	0.0446 (10)
H49A	0.3199	0.1931	0.2540	0.067*
H49B	0.3038	0.1445	0.2226	0.068*
H49C	0.1209	0.1782	0.2169	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0242 (13)	0.0180 (13)	0.0574 (17)	−0.0054 (11)	0.0016 (12)	0.0067 (12)
O12	0.0229 (13)	0.0163 (12)	0.0587 (17)	0.0041 (11)	0.0009 (12)	0.0033 (12)
O13	0.0121 (12)	0.0287 (13)	0.0428 (15)	−0.0025 (10)	0.0051 (10)	0.0041 (11)
N11	0.0124 (13)	0.0185 (14)	0.0290 (16)	0.0022 (11)	0.0028 (12)	0.0022 (12)
N12	0.0166 (14)	0.0142 (14)	0.0342 (17)	−0.0028 (11)	0.0039 (12)	0.0014 (12)
C10	0.0145 (16)	0.0170 (16)	0.0254 (18)	0.0025 (13)	0.0007 (14)	0.0028 (14)
C11	0.0186 (17)	0.0199 (18)	0.0246 (19)	−0.0018 (14)	0.0013 (14)	0.0031 (14)
C12	0.0197 (17)	0.0170 (17)	0.0253 (19)	0.0018 (14)	0.0016 (14)	0.0019 (14)
C13	0.0181 (17)	0.0204 (17)	0.0199 (18)	0.0001 (14)	0.0040 (14)	0.0014 (14)
C14	0.0178 (17)	0.0222 (18)	0.030 (2)	0.0031 (14)	−0.0003 (14)	0.0076 (15)
C15	0.0257 (19)	0.033 (2)	0.030 (2)	0.0072 (16)	0.0062 (16)	0.0036 (17)
C16	0.0221 (18)	0.0196 (17)	0.034 (2)	0.0026 (14)	0.0020 (15)	0.0005 (15)
C17	0.0282 (19)	0.0239 (18)	0.034 (2)	0.0024 (15)	0.0017 (16)	−0.0001 (16)
C18	0.034 (2)	0.036 (2)	0.031 (2)	0.0032 (17)	0.0016 (17)	−0.0021 (17)
C19	0.049 (2)	0.044 (2)	0.031 (2)	−0.008 (2)	0.0085 (19)	−0.0026 (19)
O21	0.0255 (13)	0.0195 (13)	0.0594 (18)	0.0054 (11)	0.0051 (12)	−0.0014 (12)
O22	0.0263 (13)	0.0174 (13)	0.0548 (17)	−0.0093 (11)	0.0050 (12)	0.0016 (11)
O23	0.0116 (12)	0.0298 (14)	0.0609 (18)	0.0003 (10)	0.0045 (11)	0.0016 (12)
N21	0.0112 (13)	0.0173 (14)	0.0363 (17)	0.0003 (11)	0.0014 (12)	0.0008 (13)
N22	0.0156 (14)	0.0156 (14)	0.0419 (18)	0.0008 (12)	0.0029 (13)	0.0026 (13)
C20	0.0163 (17)	0.0172 (17)	0.036 (2)	−0.0033 (14)	0.0024 (15)	−0.0010 (15)
C21	0.0222 (18)	0.0184 (18)	0.033 (2)	0.0007 (15)	0.0034 (15)	0.0019 (15)
C22	0.0177 (17)	0.0180 (18)	0.0279 (19)	−0.0008 (14)	0.0036 (14)	0.0011 (14)
C23	0.0193 (18)	0.0259 (19)	0.0276 (19)	0.0015 (15)	0.0016 (15)	0.0015 (15)
C24	0.0228 (18)	0.0249 (19)	0.039 (2)	−0.0026 (15)	0.0026 (16)	−0.0038 (16)
C25	0.039 (2)	0.040 (2)	0.034 (2)	−0.0057 (18)	0.0014 (18)	−0.0029 (18)
C26	0.0229 (18)	0.0148 (17)	0.042 (2)	−0.0019 (14)	0.0033 (16)	0.0012 (15)
C28	0.027 (2)	0.037 (2)	0.047 (2)	−0.0015 (17)	0.0081 (18)	−0.0006 (19)
C27	0.0225 (18)	0.0247 (19)	0.038 (2)	−0.0021 (15)	0.0006 (16)	−0.0020 (16)
C29	0.038 (2)	0.047 (2)	0.041 (2)	0.0018 (19)	0.0075 (19)	0.002 (2)
O31	0.0196 (12)	0.0442 (15)	0.0307 (14)	0.0000 (11)	−0.0046 (11)	−0.0138 (12)
O32	0.0178 (12)	0.0264 (13)	0.0244 (13)	0.0012 (10)	0.0041 (10)	−0.0054 (10)
O33	0.0122 (12)	0.0280 (13)	0.0314 (13)	0.0006 (10)	0.0029 (10)	−0.0023 (11)
N31	0.0132 (13)	0.0227 (15)	0.0261 (16)	−0.0002 (12)	0.0013 (12)	−0.0047 (12)
N32	0.0127 (13)	0.0194 (14)	0.0217 (15)	−0.0023 (11)	0.0001 (11)	−0.0058 (12)
C30	0.0136 (15)	0.0208 (17)	0.0227 (18)	0.0018 (13)	0.0016 (13)	−0.0041 (14)
C31	0.0220 (17)	0.0155 (16)	0.0254 (19)	−0.0024 (14)	0.0046 (15)	−0.0023 (14)
C32	0.0182 (16)	0.0111 (15)	0.0220 (18)	0.0011 (13)	0.0021 (14)	0.0017 (14)
C33	0.0170 (17)	0.0126 (16)	0.0253 (18)	0.0008 (13)	−0.0006 (14)	0.0014 (14)
C34	0.0234 (18)	0.032 (2)	0.0263 (19)	0.0000 (15)	0.0019 (15)	−0.0009 (16)
C35	0.040 (2)	0.035 (2)	0.043 (2)	0.0005 (18)	0.0047 (18)	0.0121 (19)
C36	0.0183 (17)	0.0208 (17)	0.0277 (19)	−0.0021 (14)	0.0022 (14)	−0.0057 (15)
C37	0.0286 (19)	0.0228 (18)	0.031 (2)	−0.0002 (15)	0.0069 (16)	−0.0034 (16)
C38	0.039 (2)	0.0247 (19)	0.034 (2)	−0.0001 (17)	0.0075 (17)	−0.0016 (16)
C39	0.072 (3)	0.024 (2)	0.051 (3)	0.000 (2)	0.016 (2)	0.0034 (19)
O41	0.0246 (13)	0.0357 (14)	0.0265 (14)	−0.0040 (11)	−0.0025 (11)	−0.0086 (11)
O42	0.0162 (11)	0.0292 (13)	0.0270 (13)	0.0002 (10)	0.0046 (10)	−0.0029 (11)
O43	0.0153 (12)	0.0368 (14)	0.0339 (14)	0.0001 (10)	0.0035 (10)	−0.0008 (11)
N41	0.0127 (13)	0.0262 (15)	0.0228 (15)	0.0001 (12)	0.0025 (12)	−0.0024 (12)
N42	0.0129 (13)	0.0236 (15)	0.0243 (15)	−0.0025 (11)	0.0004 (11)	−0.0074 (12)
C40	0.0190 (17)	0.0220 (18)	0.0252 (19)	0.0019 (14)	0.0045 (14)	−0.0038 (14)
C41	0.0209 (17)	0.0187 (17)	0.0227 (19)	0.0000 (14)	0.0012 (15)	−0.0018 (14)
C42	0.0173 (16)	0.0166 (16)	0.0247 (19)	0.0005 (14)	0.0020 (15)	0.0029 (14)
C43	0.0191 (18)	0.0178 (17)	0.0276 (19)	−0.0008 (14)	0.0053 (15)	0.0011 (14)
C44	0.0227 (18)	0.038 (2)	0.029 (2)	−0.0001 (16)	0.0046 (15)	−0.0025 (17)
C45	0.029 (2)	0.045 (2)	0.034 (2)	−0.0073 (18)	0.0048 (17)	0.0045 (18)
C46	0.0238 (18)	0.0244 (19)	0.031 (2)	0.0036 (15)	0.0009 (15)	−0.0072 (16)
C47	0.030 (2)	0.0265 (19)	0.0268 (19)	0.0015 (15)	−0.0025 (16)	−0.0037 (16)
C48	0.034 (2)	0.0254 (19)	0.039 (2)	0.0047 (16)	−0.0001 (17)	−0.0064 (17)
C49	0.055 (3)	0.035 (2)	0.045 (3)	0.005 (2)	0.005 (2)	0.0025 (19)

Geometric parameters (Å, º)

O11—C11	1.214 (4)	O31—C31	1.210 (4)
O12—C12	1.210 (4)	O32—C32	1.212 (3)
O13—C13	1.217 (4)	O33—C33	1.222 (3)
N11—C12	1.370 (4)	N31—C32	1.373 (4)
N11—C11	1.378 (4)	N31—C31	1.381 (4)
N11—H11	0.962 (10)	N31—H31	0.961 (10)
N12—C13	1.371 (4)	N32—C33	1.370 (4)
N12—C12	1.377 (4)	N32—C32	1.383 (4)
N12—H12	0.962 (10)	N32—H32	0.963 (10)
C10—C11	1.518 (4)	C30—C31	1.520 (4)
C10—C13	1.519 (4)	C30—C33	1.521 (4)
C10—C16	1.544 (4)	C30—C34	1.540 (4)
C10—C14	1.550 (4)	C30—C36	1.548 (4)
C14—C15	1.521 (4)	C34—C35	1.519 (5)
C14—H14A	0.9900	C34—H34A	0.9900
C14—H14B	0.9900	C34—H34B	0.9900
C15—H15A	0.9800	C35—H35A	0.9800
C15—H15B	0.9800	C35—H35B	0.9800
C15—H15C	0.9800	C35—H35C	0.9800
C16—C17	1.525 (5)	C36—C37	1.515 (4)
C16—H16A	0.9900	C36—H36A	0.9900
C16—H16B	0.9900	C36—H36B	0.9900
C17—C18	1.520 (5)	C37—C38	1.525 (5)
C17—H17A	0.9900	C37—H37A	0.9900
C17—H17B	0.9900	C37—H37B	0.9900
C18—C19	1.520 (5)	C38—C39	1.525 (5)
C18—H18A	0.9900	C38—H38A	0.9900
C18—H18B	0.9900	C38—H38B	0.9900
C19—H19A	0.9800	C39—H39A	0.9800
C19—H19B	0.9800	C39—H39B	0.9800
C19—H19C	0.9800	C39—H39C	0.9800
O21—C21	1.217 (4)	O41—C41	1.208 (4)
O22—C22	1.208 (4)	O42—C42	1.222 (4)
O23—C23	1.212 (4)	O43—C43	1.222 (4)
N21—C21	1.376 (4)	N41—C42	1.376 (4)
N21—C22	1.377 (4)	N41—C41	1.378 (4)
N21—H21	0.963 (10)	N41—H41	0.961 (10)
N22—C23	1.367 (4)	N42—C43	1.367 (4)
N22—C22	1.380 (4)	N42—C42	1.372 (4)
N22—H22	0.967 (10)	N42—H42	0.959 (10)
C20—C21	1.515 (4)	C40—C43	1.513 (4)
C20—C23	1.516 (4)	C40—C41	1.528 (4)
C20—C26	1.548 (4)	C40—C44	1.540 (4)
C20—C24	1.551 (5)	C40—C46	1.558 (4)
C24—C25	1.522 (5)	C44—C45	1.523 (5)
C24—H24A	0.9900	C44—H44A	0.9900
C24—H24B	0.9900	C44—H44B	0.9900
C25—H25A	0.9800	C45—H45A	0.9800
C25—H25B	0.9800	C45—H45B	0.9800
C25—H25C	0.9800	C45—H45C	0.9800
C26—C27	1.521 (5)	C46—C47	1.527 (5)
C26—H26A	0.9900	C46—H46A	0.9900
C26—H26B	0.9900	C46—H46B	0.9900
C28—C27	1.509 (5)	C47—C48	1.518 (5)
C28—C29	1.520 (5)	C47—H47A	0.9900
C28—H28A	0.9900	C47—H47B	0.9900
C28—H28B	0.9900	C48—C49	1.519 (5)
C27—H27A	0.9900	C48—H48A	0.9900
C27—H27B	0.9900	C48—H48B	0.9900
C29—H29A	0.9800	C49—H49A	0.9800
C29—H29B	0.9800	C49—H49B	0.9800
C29—H29C	0.9800	C49—H49C	0.9800
C12—N11—C11	126.3 (3)	C32—N31—C31	127.0 (3)
C12—N11—H11	114.0 (19)	C32—N31—H31	116.0 (19)
C11—N11—H11	119.6 (19)	C31—N31—H31	116.9 (19)
C13—N12—C12	126.3 (3)	C33—N32—C32	125.9 (3)
C13—N12—H12	117.0 (19)	C33—N32—H32	117.8 (18)
C12—N12—H12	116.6 (19)	C32—N32—H32	115.9 (18)
C11—C10—C13	114.3 (3)	C31—C30—C33	113.9 (3)
C11—C10—C16	109.6 (3)	C31—C30—C34	108.5 (3)
C13—C10—C16	107.9 (2)	C33—C30—C34	109.0 (3)
C11—C10—C14	108.0 (2)	C31—C30—C36	108.5 (3)
C13—C10—C14	107.5 (3)	C33—C30—C36	107.4 (3)
C16—C10—C14	109.5 (2)	C34—C30—C36	109.4 (3)
O11—C11—N11	120.1 (3)	O31—C31—N31	120.2 (3)
O11—C11—C10	122.0 (3)	O31—C31—C30	122.3 (3)
N11—C11—C10	117.9 (3)	N31—C31—C30	117.5 (3)
O12—C12—N11	122.4 (3)	O32—C32—N31	122.0 (3)
O12—C12—N12	121.4 (3)	O32—C32—N32	122.0 (3)
N11—C12—N12	116.3 (3)	N31—C32—N32	116.0 (3)
O13—C13—N12	119.9 (3)	O33—C33—N32	119.6 (3)
O13—C13—C10	121.9 (3)	O33—C33—C30	121.8 (3)
N12—C13—C10	118.3 (3)	N32—C33—C30	118.5 (3)
C15—C14—C10	113.2 (3)	C35—C34—C30	113.5 (3)
C15—C14—H14A	108.9	C35—C34—H34A	108.9
C10—C14—H14A	108.9	C30—C34—H34A	108.9
C15—C14—H14B	108.9	C35—C34—H34B	108.9
C10—C14—H14B	108.9	C30—C34—H34B	108.9
H14A—C14—H14B	107.8	H34A—C34—H34B	107.7
C14—C15—H15A	109.5	C34—C35—H35A	109.5
C14—C15—H15B	109.5	C34—C35—H35B	109.5
H15A—C15—H15B	109.5	H35A—C35—H35B	109.5
C14—C15—H15C	109.5	C34—C35—H35C	109.5
H15A—C15—H15C	109.5	H35A—C35—H35C	109.5
H15B—C15—H15C	109.5	H35B—C35—H35C	109.5
C17—C16—C10	114.3 (3)	C37—C36—C30	115.6 (3)
C17—C16—H16A	108.7	C37—C36—H36A	108.4
C10—C16—H16A	108.7	C30—C36—H36A	108.4
C17—C16—H16B	108.7	C37—C36—H36B	108.4
C10—C16—H16B	108.7	C30—C36—H36B	108.4
H16A—C16—H16B	107.6	H36A—C36—H36B	107.4
C18—C17—C16	112.0 (3)	C36—C37—C38	113.5 (3)
C18—C17—H17A	109.2	C36—C37—H37A	108.9
C16—C17—H17A	109.2	C38—C37—H37A	108.9
C18—C17—H17B	109.2	C36—C37—H37B	108.9
C16—C17—H17B	109.2	C38—C37—H37B	108.9
H17A—C17—H17B	107.9	H37A—C37—H37B	107.7
C17—C18—C19	112.9 (3)	C37—C38—C39	112.4 (3)
C17—C18—H18A	109.0	C37—C38—H38A	109.1
C19—C18—H18A	109.0	C39—C38—H38A	109.1
C17—C18—H18B	109.0	C37—C38—H38B	109.1
C19—C18—H18B	109.0	C39—C38—H38B	109.1
H18A—C18—H18B	107.8	H38A—C38—H38B	107.8
C18—C19—H19A	109.5	C38—C39—H39A	109.5
C18—C19—H19B	109.5	C38—C39—H39B	109.5
H19A—C19—H19B	109.5	H39A—C39—H39B	109.5
C18—C19—H19C	109.5	C38—C39—H39C	109.5
H19A—C19—H19C	109.5	H39A—C39—H39C	109.5
H19B—C19—H19C	109.5	H39B—C39—H39C	109.5
C21—N21—C22	126.6 (3)	C42—N41—C41	126.2 (3)
C21—N21—H21	117 (2)	C42—N41—H41	113.4 (19)
C22—N21—H21	117 (2)	C41—N41—H41	120.3 (19)
C23—N22—C22	126.5 (3)	C43—N42—C42	125.8 (3)
C23—N22—H22	118 (2)	C43—N42—H42	121.0 (19)
C22—N22—H22	116 (2)	C42—N42—H42	113.2 (19)
C21—C20—C23	114.7 (3)	C43—C40—C41	113.8 (3)
C21—C20—C26	108.5 (3)	C43—C40—C44	109.8 (3)
C23—C20—C26	108.1 (3)	C41—C40—C44	110.0 (3)
C21—C20—C24	107.9 (3)	C43—C40—C46	107.2 (3)
C23—C20—C24	107.2 (3)	C41—C40—C46	106.9 (3)
C26—C20—C24	110.4 (3)	C44—C40—C46	109.0 (3)
O21—C21—N21	119.8 (3)	O41—C41—N41	120.7 (3)
O21—C21—C20	122.4 (3)	O41—C41—C40	122.3 (3)
N21—C21—C20	117.9 (3)	N41—C41—C40	116.9 (3)
O22—C22—N21	122.4 (3)	O42—C42—N42	122.3 (3)
O22—C22—N22	121.8 (3)	O42—C42—N41	121.1 (3)
N21—C22—N22	115.9 (3)	N42—C42—N41	116.6 (3)
O23—C23—N22	120.1 (3)	O43—C43—N42	119.9 (3)
O23—C23—C20	121.8 (3)	O43—C43—C40	121.7 (3)
N22—C23—C20	118.2 (3)	N42—C43—C40	118.3 (3)
C25—C24—C20	113.9 (3)	C45—C44—C40	113.5 (3)
C25—C24—H24A	108.8	C45—C44—H44A	108.9
C20—C24—H24A	108.8	C40—C44—H44A	108.9
C25—C24—H24B	108.8	C45—C44—H44B	108.9
C20—C24—H24B	108.8	C40—C44—H44B	108.9
H24A—C24—H24B	107.7	H44A—C44—H44B	107.7
C24—C25—H25A	109.5	C44—C45—H45A	109.5
C24—C25—H25B	109.5	C44—C45—H45B	109.5
H25A—C25—H25B	109.5	H45A—C45—H45B	109.5
C24—C25—H25C	109.5	C44—C45—H45C	109.5
H25A—C25—H25C	109.5	H45A—C45—H45C	109.5
H25B—C25—H25C	109.5	H45B—C45—H45C	109.5
C27—C26—C20	112.7 (3)	C47—C46—C40	117.0 (3)
C27—C26—H26A	109.0	C47—C46—H46A	108.1
C20—C26—H26A	109.0	C40—C46—H46A	108.1
C27—C26—H26B	109.0	C47—C46—H46B	108.1
C20—C26—H26B	109.0	C40—C46—H46B	108.1
H26A—C26—H26B	107.8	H46A—C46—H46B	107.3
C27—C28—C29	111.9 (3)	C48—C47—C46	112.7 (3)
C27—C28—H28A	109.2	C48—C47—H47A	109.0
C29—C28—H28A	109.2	C46—C47—H47A	109.0
C27—C28—H28B	109.2	C48—C47—H47B	109.0
C29—C28—H28B	109.2	C46—C47—H47B	109.0
H28A—C28—H28B	107.9	H47A—C47—H47B	107.8
C28—C27—C26	113.5 (3)	C47—C48—C49	113.3 (3)
C28—C27—H27A	108.9	C47—C48—H48A	108.9
C26—C27—H27A	108.9	C49—C48—H48A	108.9
C28—C27—H27B	108.9	C47—C48—H48B	108.9
C26—C27—H27B	108.9	C49—C48—H48B	108.9
H27A—C27—H27B	107.7	H48A—C48—H48B	107.7
C28—C29—H29A	109.5	C48—C49—H49A	109.5
C28—C29—H29B	109.5	C48—C49—H49B	109.5
H29A—C29—H29B	109.5	H49A—C49—H49B	109.5
C28—C29—H29C	109.5	C48—C49—H49C	109.5
H29A—C29—H29C	109.5	H49A—C49—H49C	109.5
H29B—C29—H29C	109.5	H49B—C49—H49C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O13^i	0.96 (1)	1.89 (1)	2.854 (3)	178 (3)
N12—H12···O22^ii	0.96 (1)	1.88 (1)	2.829 (3)	171 (3)
N21—H21···O23^i	0.96 (1)	1.90 (1)	2.857 (3)	171 (3)
N22—H22···O12	0.97 (1)	1.91 (1)	2.843 (3)	161 (3)
N31—H31···O33^ii	0.96 (1)	1.89 (1)	2.854 (3)	176 (3)
N32—H32···O42	0.96 (1)	1.93 (1)	2.877 (3)	167 (3)
N41—H41···O43^i	0.96 (1)	1.90 (1)	2.858 (3)	178 (3)
N42—H42···O32	0.96 (1)	1.91 (1)	2.861 (3)	170 (3)
C36—H36B···O31^iii	0.99	2.40	3.318 (4)	155

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1.